EP0944899B1 - Double-bond shifts of substituted (4n)-annulenes for information storage and data processing - Google Patents
Double-bond shifts of substituted (4n)-annulenes for information storage and data processing Download PDFInfo
- Publication number
- EP0944899B1 EP0944899B1 EP96940064A EP96940064A EP0944899B1 EP 0944899 B1 EP0944899 B1 EP 0944899B1 EP 96940064 A EP96940064 A EP 96940064A EP 96940064 A EP96940064 A EP 96940064A EP 0944899 B1 EP0944899 B1 EP 0944899B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- group
- substituted
- conjugation
- heptalene
- annulenes
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C69/753—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring of polycyclic acids
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/004—Recording, reproducing or erasing methods; Read, write or erase circuits therefor
- G11B7/0045—Recording
- G11B7/00455—Recording involving reflectivity, absorption or colour changes
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/004—Recording, reproducing or erasing methods; Read, write or erase circuits therefor
- G11B7/0065—Recording, reproducing or erasing by using optical interference patterns, e.g. holograms
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
- G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/146—Laser beam
Definitions
- the present invention is related to a method for information storage and data processing comprising the step of thermo inducing or photo inducing double-bond shifts (DBS) in substituted [4n]-annulenes, which are substituted by at least one group comprising an extended conjugated ⁇ -electron system which is in conjugation with the ⁇ -electron system of the [4n]-annulene core, thus generating transitions between two different conjugation states with at least one substituent.
- the two different conjugation states are the conjugation on-state and conjugation off-state of the annulene core ⁇ -electrons with the substituent ⁇ -electrons.
- the present invention is furthermore related to novel substituted [4n]-heptalenes being optically and/or thermally switchable, based on thermal or photochemical double-bond shifts (DBS) as well as methods for their preparation.
- DBS thermal or photochemical double-bond shifts
- Molecular and supramolecular devices e.g. molecular switches, photo-sensible complexants or molecular wires are currently of utmost interest, because they provide a novel approach for performing a variety of different tasks, like for instance photo-induced ion transport, photo-induced catalysis or electron transport within molecular wires.
- the function performed by a molecular or supramolecular device results from elementary properties performed by the components, such as photoactive, electroactive or ionoactive components, depending on whether they could operate with photons, electrons or ions.
- a cis/trans isomerisation can be induced within the photo-sensitive molecule, thus leading for instance to markedly different complexing properties of the entire molecule.
- suitable guests e.g. ions
- Examples of known molecular and supramolecular devices e.g. photo-induced ion transport systems are described in F. Vögtle, Supramoleculare Chemie, Teubner vesselsbücher, Stuttgart 1992.
- Optical computing Another field of interest in connection with supramolecular or molecular devices is related to data processing by means of optical computing.
- Usual data processing is essentially performed with magnetic layers and/or digital electronic computers consisting of a large collection of interconnected switches, gates and memory elements called “flip-flops".
- Logic operations are performed by controlling the flow of electrons between these various components.
- Optical computers also use switches, gates and flip-flops in their logic operations, but the design of these devices are very different.
- the purpose of a switch is to make or break a connection between one or more transmission paths. If a switch controls the connection from just one path to another path, it is called a 1 x 1 switch.
- Other possibilities include 2 x 2, n x n, n x m switches whereby n and m could be any integer.
- switches can be built from modulators using opto-mechanical, electro-optic, acusto-optic, magnetic-optic and other techniques.
- a well-known example represents the Mach-Zehnder interferometer in which the refractive index of one leg is electro-optically controlled and which is used as a 1 x 1 optical switch. By modulating the relative phase of the divided wavefronts as they pass through the interferometer, they can be constructively or destructively recombined at the output, thus creating an on-state or an off-state.
- optical switching design is the directional coupler which represents a 2 x 2 switch. Again, the electro-optic control of the refractive index of these devices shifts them between two states: cross and bar. Further modulators are known, whereby the on/off state is provided by liquid crystals or acousto-optic switches.
- optical switches are electrically or magnetically controlled. With the help of certain non-linear optical effects, all optical switches can be constructed as well. For example, by using the optical Kerr effect, it is possible to transform the above mentioned Mach-Zehnder interferometer into an all-optical switch.
- optical disks and holograms Another feature of data processing is data storage by optical disks and holograms.
- the information on optical disks e.g. CD-disks
- CD-disks e.g. CD-disks
- CW-light from a low power diode laser is tightly focused onto the pits by a short-focal-length objective mounted on a movable read head.
- the information stored by a binary code consisting of pits of different lengths can be repeatedly read-out.
- the underlying material must be modifiable by an external source so to apply an erasable or durable distribution of physical properties that could be determined by appropriate technical means for read-out purposes.
- Said physical properties could comprise among others optical properties, e.g. the refraction index, magnetic properties or mechanical properties like the different length of pits (e.g. in CD-disks).
- One aspect of the present invention was to provide a novel material, i.e. novel chemical compounds, which displays two different states that can be determined for read-out purposes.
- a further aspect of the present invention was to provide a method of information storage and data processing using said novel chemical compounds.
- Still a further aspect of this invention was to provide novel photo-sensitive (4n)-annulene systems that are capable of thermal or photochemical double-bond shifts thus providing the possibility of switch from one conjugation state to another under the influence of an external source, e.g. light or heat.
- an external source e.g. light or heat.
- Another further aspect of the present invention was to provide a method for preparing novel (4n)-annulenes that are capable of thermal or photochemical double-bond shifts.
- the reversible interconversion of said double-bond shifted (DBS) isomers represents ⁇ -skeletal rearrangement that may be induced thermally or photochemically.
- the energy barriers separating the twisted double-boat forms of the two DBS isomers of heptalenes and tub forms of the two DBS isomers of cyclooctatetraenes are mainly dependent on the number and bulkiness of contiguous substituents at the two annulenes, whereby, in the case of heptalenes, the size and number of the peri-substituents are specially relevant. Two typical examples are shown on scheme 1:
- the thermal DBS process in heptalenes is, in general, not competed by other thermal reaction.
- heptalene-1,2-dicarboxylates may suffer a ⁇ -skeletal rearrangement into heptalene-1,3-dicarboxylates and may also disintegrate to azulene-dicarb6xylates.
- cyclooctatetraenes according to the D 2d symmetry of their [4n]-core, are not inherently chiral, but may appear in antipodes due to their substitution pattern.
- the E a values of the racemization of optically active cyclooctatetraenes which correspond to a net inversion of their tub form, are normally smaller than those for the DBS process or may become quite similar for both envisaged reactions.
- a reversible disrotatory ring closure of cyclooctatetraenes can take place to yield bicyclo[4.2.0]-octatriene derivatives (e.g. 2a' is at room temperature in thermal equilibrium with a small amount of its bicyclic valence isomer, namely 1,2,7,8-tetramethylbicyclo-[4.2.0]-octa-2,4,7-triene.
- the DBS process can clearly be observed separately from the other thermal reactions.
- heptalenes offer the advantage that the DBS process takes place here with the lowest activation energy and only low energy irradiations ( ⁇ > 360 nm) are necessary for the photochemical variant of the DBS process.
- the different optical properties (e.g. UV/Vis-absorption) of the different valence isomers are also known.
- thermochromic system based on cyclic double-bond shifts in heptalenes was, in principle, described by H.-J. Hansen in Chimia 50, (1996), No 7/8, page 341.
- said document does not provide sufficient information on the synthesis of such compounds nor does it provide any information on the possibility to exploit for data processing the fact that different physical properties (UV/Vis absorption) arises from the double bond shifts.
- the present invention provides a method for information storage and data processing comprising the step of thermo-inducing or photo-inducing double-bond shifts (DBS) in substituted [4n]-annulenes which are substituted by at least one group comprising an extended conjugated ⁇ -electron system which is in conjugation with the ⁇ -electron system of the [4n]-annulene core, thus generating transitions between two different conjugation states with at least one substituent.
- DBS thermo-inducing or photo-inducing double-bond shifts
- substituted [4n]-heptalenes of the general formula (I) or (II) being optically and/or thermally switchable, based on thermal or photochemical double-bond shifts (DBS), whereby C 1 and C 2 represent independently from each other a hydrogen atom, a substituted or unsubstituted C 1 -C 12 -alkyl group, a substituted or unsubstituted C 1 -C 12 -alkoxy group, a substituted or unsubstituted aryl-C 1 -C 12 -alkyl group, a substituted or unsubstituted C 1 -C 12 -alkenyl group, a substituted or unsubstituted C 1 -C 12 -conjugated alkenyl group, a substituted or unsubstituted C 1 -C 12 -alkinyl group, a substituted or an unsubstituted phenyl group, a substituted or an
- said [4n]-heptalenes can comprise at least one further substituent R being selected from the above indicated groups with n being 0-8, provided that if one of the at least one fur-ther substituents R is an isopropyl group at the position 9 of the heptalene ring, the substituent at the position 6 must not be a methyl group, and with the proviso that heptalenes having the following formulae including their valence isomers are excluded: wherein Ar 1 is phenyl, 4-chloro phenyl or 4-methoxy phenyl, wherein Ar 2 is phenyl or 4-methoxy phenyl and wherein R 1' and R 2' are alkyl, aralkyl or aryl, which may be substituted, but the case wherein R 1' and R 2' are both alkyl is excluded and R 3' and R 4' are
- the chemical compounds according to the present invention being optically and/or thermally switchable, due to thermal or photochemical double-bond shifts (DBS), usable for data processing, are comprising substituted [4n]-annulenes, which comprise at least one substituent displaying an extended conjugated ⁇ -electron system which is in conjugation with the ⁇ -electron system of the [4n]-annulene core.
- Preferred [4n]-annulenes are bicyclic [4n]-annulenes, i.e. fused [4n]-annulene systems, like heptalene.
- C 1 and C 2 represent ⁇ -substituents which are capable of conjugation, whereas R represents non-conjugative substituents (e.g. alkyl groups) that could moderate via their steric interactions the activation energy of the thermal DBS process.
- the term CS denotes the conjugative switch in local 1,2- (1,2-CS) or 1,4-relation (1,4-CS) at the [4n]-perimeter.
- the on-state condition means that the substituents C 1 and C 2 are in conjugation via the ethylene or s-cis-buta-1,3-diene substructure of the [4n]-annulene core.
- the off-state condition means an interruption of the direct conjugation of the substituents C 1 and C 2 .
- the two distinct conjugation states differ in their ⁇ -electron conjugation of the ⁇ -system of the heptalene core with the substituent ⁇ -system, in as far as the conjugation of the phenyl ⁇ -electrons are better in a s-trans-cis-1,3-diene-conjugation with the ⁇ -system of the heptalene core 7a' along the annulene ring atoms C 1 to C 4 , whereas in 7b' said butadiene conjugation along the annulene ring atoms C 1 to C 4 there is not a s-cis-buta-1,3-diene-conjugation, but only the less favorable C 3 -C 4 -atom allyl conjugation, respectively a C 1 -C 2 -atom vinyl conjugation.
- the corresponding thermal and photochemical DBS process can be utilized as a molecular conjugative switch (CS) to bring on- or off-conjugation between ⁇ -substituents (C 1 , C 2 ), placed in 1,2 or 1,4 relation at the [4n]-annulene core.
- CS molecular conjugative switch
- Most obvious are the possible 1,2-CS systems. However, they have the disadvantage that the C 1 and C 2 substituents are close together in the on-state, which may lead to steric interactions between C 1 and C 2 , thereby forcing one or both ⁇ -substituents out of conjugation.
- the 1,4-CS systems are more preferred, 1,4-C ⁇ 2,5-C where conjugation between C 1 and C 2 can be realized via an s-cis-butadiene substructure.
- conjugation via the s-cis-butadiene subunits is not reduced by more than a fifth, assuming that C 1 and C 2 are in an optimal conformation (i.e. ⁇ near 0 or 180°) with respect to "their" heptalene double bonds in the on-state.
- the systematically possible 1,4-CS arrangement 5,10-D ⁇ 1,6-D and 2,10-E ⁇ 1,9-E are less effective as conjugative switches due to the unfavorable ⁇ av of the involved s-trans-butadiene subunits which vary in the range of 114-124° (D-type) and 118-127° (E-type) for heptalenes bearing three or four peri-substituents (see scheme 4) and will reduce conjugation by up to 60%.
- the situation is similar to higher substituted cyclooctatetraenes where X-ray crystal diffraction analyses reveal that the average torsion angles between the ethylene subunits fluctuate in the range of 64 to 69°. Therefore, cyclooctatetraenes are only useful as switches in the 1,2-CS setting.
- transition state of the DBS process in heptalenes is non-planar with a maximum symmetry of D 2 of the heptalene core as it is demonstrated by the isoconfigurational transformation of optically active heptalenes.
- ⁇ -SCF-force field calculations by Lindner and Flöter are in agreement with these findings.
- the on-state DBS-isomer wherein the perimeter substituent displaying an extended ⁇ -electron system being in s-trans position relative to the core butadiene ⁇ -electron system, is not switched to a corresponding off-state DBS-isomer wherein said perimeter substituent displaying an extended ⁇ -electron system is in s-cis position relative to the core butadiene ⁇ -electron system, but remains in an s-trans position.
- Figures 1A and 1B provide an example of such a UV/VIS spectra of the two DBS-isomers 16a, respresenting the off-state of this 1,4-CS system and 16b being equivalent with the on-state.
- the [4n]-annulene in figure 1A and 1B is a heptalene, having two substituents that display an extended ⁇ -electron system. Said substituents are both a phenyl-trans-butadiene group that are in 1,4-relation to each other.
- the three main heptalene bands of said figure 1A are clearly recognizable in the spectrum of 16a . Band I appears as a weak shoulder at ca. 430 nm, followed by the much more intense shoulder of the band II at ca.
- the two states of the 1,4-CS system 16a ⁇ 16b can also be recognized with the bare eye.
- an orange-colored hexane solution of the thermal equilibrium mixture of 16a and 16b is irradiated at ca. 0° with (439 ⁇ 10) nm-light in a vessel and is kept in the dark in a second vessel only the solution in the irradiated vessel turns to pure yellow which is clearly distinguishable from the still orange color of the protected solution.
- conjugation on-state is the result of double-bond shifts (DBS) resulting in different UV/VIS spectra of the DBS isomers of [4n]-annulenes
- conjugation on-state can be switched to a conjugation off-state and vice versa
- substitution pattern on the heptalene system can be tailored to provide a desired thermal activation barrier.
- Said carrier matrix can comprise a low-melting glass or polycarbonates, polyacetates, polymethacrylates, polystyrenes and copolymers thereof, as well as copolymers with a polymerisable [4n]-annulene.
- a binary code can be set-up and which is consisting in the conjugation on-state and the conjugation off-state.
- the [4n]-annulene e.g.
- the desired data is applied by means of a suitable low-energy diode laser of a distinct wavelength, while simultaneous irradiation with photochemically active light takes place, if required, whereby locally the conditions are created for the double bond shift entailing the switch from the conjugation on-state to the conjugation off-state and once the laser moves to the next (neighboring) place, upon cooling down, the thus generated conjugation switch is, as matter of fact, freezed in the solid state, so that no reverse switching from the conjugation off-state to conjugation on-state is possible any more.
- the present invention provides a data storage material based on locally defined conjugation states, thus generating a binary code, like conventional CDs.
- a low melting [4n]-annulene has to be used.
- the photo-induced double-bond shift (DBS) has to be performed after prior softening of said solid [4n]-annulenes (e.g. in crystalline form) so that the mobility of said [4n]-annulene, e.g. heptalene, is increased. In a semi-molten state or in a molten state, said [4n]-annulenes do undergo said photo-induced double-bond shift (DBS).
- Still another possibility of data storage is the generation of a matrix comprising tiny liquid drops containing the solubilized [4n]-annulenes and which are embedded in a solid matrix.
- a drops-containing matrix provides the possibility of the application of distinguishing signs upon all kinds of documents, bank-notes or credit cartes.
- the distinguishing sign comprising said [4n]-annulene, e.g. heptalene, according to the present invention is bleached upon exposition to an appropriate light, due to the switching from the conjugation on-state being colored to the conjugation off-state being bleached.
- the reverse switch then takes place automatically upon exposing said sign to the normal ambient light, where the natural equilibrium is re-adjusted.
- the change of color upon exposition to light provides a non-falsiable, non-copyiable distinguishing sign for said documents.
- the heptalene plus matrix system as a gatable (vide supra) photochromic material for holographic storage.
- An object and a reference, beam of a photochemically active wavelength are brought to interference in a cube or thick layer of a glass or polymer, containing a suitable [4n]-annulene, e.g. a heptalene, kept at a temperature sufficient to permit the generation of a photochemicallly generated holographic interference pattern.
- the hologram thus generated, becomes insensitive to light and can be read-out in the usual manner.
- a thermal holographic interference pattern can be generated by a pulsed object and reference beam in a heptalene plus matrix system which either contains, at the outset, a distribution of on states and off-states being not in thermal, or which is irradiated simultaneously under light of a photochemically active wavelength.
- a multitude of [4n]-annulene molecules are arranged in a 1-dimensional, or 2-dimensional or 3-dimensional way wherein said conjugation states are spacially non-uniformly modulated.
- a carrier system like a film, a disk or a cube that allows the modulation of a multitude of the corresponding [4n]-annulene molecules for the permanent, or erasable, storage of their corresponding conjugative state.
- a defined distribution thereof is generated upon said carrier that corresponds to the information that is intended to be stored.
- the matrix described above simultaneously serves as such a carrier.
- a further step is performed wherein at least one of the optical, electric or magnetic properties being attributable to said conjugation states is determined and processed.
- optical properties are light absorption and emission, the index of refraction, non-linear responses, chiro-optical properties (in chiral systems).
- response of optical properties to external influences can be harnessed, e.g. applied electrical/magnetic fields, stress.
- the "Kerr-effect" which is well known to the man of the art, is to be mentioned in this respect.
- magnetic and/or electric properties are electrical conductivity (conducting polymer with inserted [4n]-annulene molecules) and magnetic susceptibility.
- said conjugation states of the [4n]-annulenes are determined by a suitable read-out step.
- said read-out step is an optical read-out step.
- Possible applications of devices making use of the switchability of double-bond shifts related conjugation states comprise among others optical recording materials, i.e. means for the optical recording of information, or means for the optical switching and computing, or optically switched photoconductive polymers.
- optical recording materials i.e. means for the optical recording of information, or means for the optical switching and computing, or optically switched photoconductive polymers.
- a multitude of [4n]-annulene molecules are arranged in a 2-dimensional way whereby said conjugation states are spacially non-uniformly modulated.
- a conformationally restricted matrix system is generated by modulating said conjugation states.
- An example for an optical recording material is a compact disk (CD): Conventional recordable CD's are classified as either write-once-read many, or erasable.
- Write-once optical storage commonly called write-once-read-many (WORM) is designed for archival data storage applications, especially those that require an indelible trail, such as birth, medical and insurance records. Consequently, WORM disks are constructed with permanence and storage capacity in mind.
- Erasable and fully rewritable optical disks can be easily obtained by locally exposing the matrix containing the [4n]-annulene molecules to a suitable laser, thus softening slightly the polymer matrix which provides the condition for the switchability between said conjugation states and whereby a suitable wavelength is opted for making sure that said conjugation switch is actually taking place.
- a further preferred embodiment of data processing by means of [4n]-annulene molecules consists in arranging a multitude of [4n]-annulene molecules in a 3-dimensional way whereby said conjugation states are spacially non-uniformly modulated, thus generating a holographic grating by modulating said conjugation states.
- the 3-dimensional modulation of [4n]-annulene molecules for data processing for the commonly called holographic memory, or, conversely, a holographic correlator.
- a further possibility is the optical computing, where the spatial light modulator frequently found in programmable parallel processing arrangements is based on a film containing the [4n]-annulenes, preferably the heptalenes, according to the present invention.
- the pixel pattern in such a film is defined by the [4n]-annulene, preferably heptalene, molecules being either in the conjugation on-state or conjugation off-state.
- the pattern is imprinted by a beam of visible or near IR-light which passes through said film, either as a spatial intensity variation or a spatial variation of the phase of the electromagnetic radiation.
- Switching of the pattern is accomplished by switching the distribution of conjugation on-states and conjugation off-states of the the substituted [4n]-annulenes, preferably substituted heptalenes, molecules by any of the methods outlined in the preceeding sections dealing with data storage.
- a holographic pattern can be set-up in a film of appropriate thickness or in a volume containing [4n]-annulene, preferably heptalene, molecules by bringing to interference a reference and an object beam in said volume.
- Such a hologramm is of a lasting or transitory nature depending on the choice of the substituted [4n]-annulene, preferably substituted heptalene system according to the present invention.
- the absorption pattern, or the index of refraction pattern, associated with such a hologram can be used for the parallel routing and distribution of information carrying light. This latter term is always meant to include near and near IR-radiation.
- a further function which is performed by a system containing the substituted [4n]-annulenes, preferably substituted heptalenes according to the present invention, due to its light by light modulating capacity, is that of a fully optical flip-flop.
- a preferred system is a liquid film containing substituted [4n]-annulene, preferably substituted heptalene, molecules with the conjugation on-state being thermally more stable than the conjugation off-state, but with rapid interconversion of the two states at the chosen temperature.
- the film becomes bleached in proportion to the intensity of the incident beam.
- the amount of the transmitted light is a non-linear function of the amount of the incident light, and by feeding back a part of the transmitted light into the beam of the incident light, an optical flip-flop with an opaque and bleached state is realized.
- the system is similar to an optical saturable absorber with two crucial advantages: bleaching can be essentially complete (saturable absorber: max 50%) and the lifetime of the bleached state is determined by a thermally controllable interconversion rate between for instance the [4n]-annulene, preferably heptalene, conjugation on-state and conjugation off-state, and not by the radiative lifetime of the electronically excited state.
- bleaching can be essentially complete (saturable absorber: max 50%) and the lifetime of the bleached state is determined by a thermally controllable interconversion rate between for instance the [4n]-annulene, preferably heptalene, conjugation on-state and conjugation off-state, and not by the radiative lifetime of the electronically excited state.
- systems working with low light levels can be designed by means of the [4n]-annulene, preferably heptalene, molecules according to the present invention.
- Still another possibility for application is a material comprising basically two components, whereby one component provides the two conjugation states (on-state and off-state) having different optical properties and which consists of the inventive substituted [4n]-annulenes.
- the second component comprises preferably a system that is performing a distinct function, e.g. electron transport, complexation or catalysis, but which depends on the switchable optical responses of the first component.
- a supramolecular system can be set-up, whereby one component is switching the conductive, complexing or catalytical activities of the second component.
- the two-component system could also be realized in one substituted [4n]-annulene system only.
- those contiguous substituents within the [4n]-annulene system which do not provide ⁇ -conjugation e.g. alkyl groups
- the conformational switch can be influenced by a first wavelength, whereas the double bond shift is performed by a second wavelength.
- the double-bond shifts could be triggered by means of a second light source of ⁇ being at about 430 nm, instead of using heat to provide conformational mobility.
- said photosensitive contiguous substituents are selected and adjusted in a way that one of said two conformational situations within said perimeter substituent allows the double-bond shifts of the heptalene, whereas the other does not.
- This embodiment can be employed in cases where the required heating to increase the conformational mobility of said heptalenes is not practicable, for instance because the annulenes are not stable under the given thermal circumstances, or higher speed or lower energy input is desirable.
- the present invention also provides a method to read out said data.
- said two conjugation states provide distinguishable physical properties. Notably optical properties, like the index of refraction or the absorption of both conjugative states can be used for read-out purposes.
- a IR-laser is used for scanning the surface of a disk, whereupon the data is recorded or stored like on a conventional disk, and a further means detecting and processing the difference in refraction or absorption of the spatially non-uniformly modulated conjugation states provides the actual data processing.
- the spacially non-uniformely modulated conjugation states can be used for optical recording of information or for optical switching and computing, as well as light modulating purposes.
- novel substituted [4n]-heptalenes of the formula (I) or (II), as defined herein.
- said further substituents are selected from the group comprising substituted or unsubstituted C 1 -C 12 -alkyl groups or photoactive diazo-containing groups, like azobenzen. Said further substituents are preferred in order to provide for the conformational switchability of the annulene, i.e. in order to adjust the activation barrier for said conformational switchability.
- the [4n]-heptalenes are forming a carrier matrix together with further copolymers, they preferably contain polymerisable substituents.
- copolymers with a polymerisable [4n]-annulene e.g.
- Particularly preferred heptalenes are those which carry extended ⁇ -substituents on the positions 1 and 4, notably ⁇ -substituents carrying themselves donor-acceptor groups, e.g. a butadienyl-4-(p-nitrophenyl) substituent, or a butadienyl-4-(p-methoxyphenyl) substituent, or alternatively one donor-substituted ⁇ -substituent in the position 1 and and acceptor-substituted ⁇ -substituent in the position 4.
- donor-acceptor groups e.g. a butadienyl-4-(p-nitrophenyl) substituent, or a butadienyl-4-(p-methoxyphenyl) substituent, or alternatively one donor-substituted ⁇ -substituent in the position 1 and and acceptor-substituted ⁇ -substituent in the position 4.
- the conformational switchability has therefore to be restricted. This can be realized by adding further C 1 -C 12 -alkyl groups. For instance, through multiple methyl substituents on the positions 6-10, preferably with a methyl group on each of said positions, the conformational switchability can be substantially reduced, thus leading to high activation barriers for the transfer from one DBS-isomer to another.
- a further aspect of the present invention is the preparation of novel heptalenes substituted with extended ⁇ -systems.
- a preferred method for the preparation of substituted [4n]-heptalenes of the formula (I) or (II) whereby C 1 , C 2 , R and n are as above defined comprises the steps of
- a heptalene-4,5-dicarboxylate carrying a methyl substituent at the position 1 of the heptalene ring is obtained.
- Heptalenedicarboxylates are readily available through Diels-Alder reaction of activated acetylenes with suitable azulenes.
- the introduction of an alkyl group around the heptalene core, preferably in 1 or 2-position is possible and furthermore 2 carboxylic acid or ester groups are also incorporated, preferably in 4 and 5-position.
- perimeter carboxylate substituents do already represent substituents that could be in conjugation with the ⁇ -electron system of the heptalene ring, it is preferred to transform at least one of said carboxylic groups into a substituent displaying an extended ⁇ -electron system, or to transform another group that was entered by the preliminary Diels-Alder reaction into a suitable substituent displaying an extended ⁇ -electron system.
- the methyl group in position 1 being transformed into a substituent displaying an extended ⁇ -electron system, plus one carboxylic ester group, preferably in the 4-position, being also transformed into a substituent displaying an extended ⁇ -electron system provide a system wherein the butadiene subunit within the annulene core is in an extended conjugation with the ⁇ -substituents of the position 1 and 4.
- guaiazulene (10.0 g, 0.05 mol) and dimethyl acetylenedicarboxylate (ADM; 18.0 ml, 0.15 mol) are dissolved in toluene (150 ml) and heated in a closed vessel at 130°C/24 h. Toluene is distilled off and the residue dissolved in a minimum amount of Et 2 O. At 4°C, 2b deposites in yellow crystals. The residue of the mother liquor is chromatographed on silica gel (hexane/Et 2 O 4:1) to yield a second batch of 2b . In total, 11.6 g (68%) of pure 2b are obtained; m.p. 147°C.
- the established through-conjugation in 1-substituted heptalene-4,5-dicarboxylates is also effective chemically, i.e., it is expressed in a higher acidity of the H-atoms of the Me group at C(1) as compared to that of the H-atoms of the Me group at C(6) in 2b . Indeed, the reactivity differences of the two Me groups in 2b are striking.
- N-bromosuccinimide (NBS) in boiling CCl 4 leads mainly to the introduction of a Br-substituent at the 'olefinic' Me group at C(6)
- the reaction of 2b with t-BuOK in THF at -78° in the presence of hexachloroethane as electrophilic chlorinating agent gives exclusively, in excellent yields, the 5-chloromethylheptalene 5b.
- Example 2 Preparation of dimethyl 6,8,10-trimethyl-4-phenylheptalene-1,2- and dimethyl 6,8,10-trimethyl-2-phenylheptalene-4,5-dicarboxylate ( 7a' and 7b' ).
- 4,6,8-Trimethyl-2-phenylazulene (0.292 g, 1.00 mmol) and dimethyl acetylenedicarboxylate (0.215 g; 1.50 mmol) are heated in decalin (4 ml) for 5 h at 190°. Further dimethyl acetylenedicarboxylate (0.215 g; 1.50 mmol) is added and the heating is continued for additional 3 hours until most of the azulene is consumed (TLC control). Thereafter, all volatile material is removed at 50°/HV and the residue subjected to a column chromatography on silica gel with hexane/Et 2 O (7:3) as eluant. Four fractions are obtained.
- the first fraction contained none-consumed azulene (0.030 g; 10%)
- the second fraction contained dimethyl (E)-1-(4,6,8-trimethyl-2-phenylazulen-1-yl)ethene-1,2-dicarboxylate ((E)- 20' ) (0.015 g; 4%)
- the third one a 23:77 mixture of 7a' / 7b' (0.140 g; 36%)
- the last fraction contained dimethyl 4,6,8-trimethylazulene-1,2-dicarboxylate (0.034 g; 12%).
- the salt 7b (4.72 g, 6.48 mmol) and cinnamaldehyde (8.6 g, 65 mmol) are stirred under an atmosphere of Ar at room temperature/3 d in the 1:1 two-phase system CH 2 Cl 2 /2N aq.NaOH (600 ml). The originally developed deep-red color changes to orange within 3 d. The basic phase is extracted with CH 2 Cl 2 and the extracts washed with water and dried (Na 2 SO 4 ).
- Example 4 Double-bond shift of dimethyl 6,8,10-trimethyl-5-[(E)-2-phenylethenyl]-heptalene-1,2- and dimethyl 6,8,10-Trimethyl-1-[(E)-2-phenylethenyl]-heptalene-4,5-dicarboxylate ( 11a' and 11b' , respectively).
- Heating of 11b' at 60-80° do not lead to the formation of its DBS isomer 11a' (HPLC and 1 H-NMR prove; limit of detection of 11a ' ⁇ 0.5%).
- irradiation of 11b' in hexane with light of a 366-nm-fluorescence tube establishes a photostationary state consisting of 68% of 11b' and 32% of 11a'.
- the photostationary state could be shifted to 20% of 11b' and 80% of 11a' when the irradiation is performed through a cut-off filter of an aqueous 1 N NaNO 2 solution ( ⁇ > 400 nm; with a high-pressure mercury lamp). Heating of this solution at 60° transformes 11a' quantitatively again into 11b'.
- Example 5 dimethyl (-)-(P)- and (+)-(M)-6,8,10-trimethyl-5-[(E)-2-phenylethenyl]-heptalene-1,2-dicarboxylate ((-)-(P)- 11a' and (+)-(M)- 11a'
- Example 6 dimethyl (-)-(P)- and (+)-(M)-6,8,10-Trimethyl-1-[(E)-2-phenylethenyl]-heptalene-4,5-dicarboxylate ((-)-(P)- 11b' and (+)-(M)- 11b' )
- CD-spectrum (circular dichroism) of (-)-(P)- 11b' (hexane; extrema in ⁇ with respect to ⁇ 2.6915 ⁇ 10 4 lmol -1 cm -1 of pure (MP)- 11b' in hexane): 550 (0), 402.6 (-42.70), 348.6 (0), 306.4 (50.60), 263.8 (Min, 8.1), 251.6 (24.66), 237.0 (Min, 2.4), 222.2 (22.50), 210.6 (0);
- Example 7 Preparation of methyl 1,6-dimethyl-9-i-propyl-[(E)-4-phenyl-butandienyl]heptalene-5-carboxylate and methyl 1,6-dimethyl-9-i-propyl-[(Z)-4-phenyl-butandienyl]heptalene-5-carboxylate
- Carbaldehyde 11b is characterized by its 1 H-NMR spectrum (CDCl 3 ), showing the signal for the H-atom of the carbaldehyde group at 9.37 ppm and the signal for the H-atoms of MeOCO-C(5) at 3.71 ppm.
- the known lactone 12b is also characterized by its reported 1 H-NMR spectrum.
- the mixture is dissolved in hexane/Et 2 O 1:1 (10 ml) and stirred with a catalytic amount of I 2 at room temperature/6 h, whereby the cis-isomers are isomerized quantitatively into the thermal equilibrium mixture consisting of 70% 13a and 30% of 13b .
- Example 8 Preparation of dimethyl 5-(4-Methoxyphenyl)-6,8,10-trimethylheptalene-1,2-dicarboxylate and dimethyl 1-(4-Methoxyphenyl)-6,8,10-trimethylheptalene-4,5-dicarboxylate ( 10a' and 10b' , respectively)
- Heptalene 10b' in hexane does not give its DBS isomer 10a' on heating. However, on irradiation with 366-nm-light of a fluorescence tube, it easily rearranges to 10a' and forms a photostationary state which consists in 62% of 10b' and 38% of 10a'.
- the 4-carboxylic acid (0.13 g, 0.30 mmol) is dissolved in MeCN (0.8 ml) and added at 0°C to the iminium salt formed in MeCN (1.7 ml) from DMF (0.072 g, 0.56 mmol) and oxalyl chloride (0.143 g, 1.95 mmol) at 0°C. After 5 min at 0°C, MeOH (5 ml) is added and then water (5 ml). The organic material is extracted with Et 2 O and the extracts washed with water and dried (Na 2 SO 4 ).
- Carbaldehyde 15b The reduction of the pseudo-ester 14b (1.50 g, 3.30 mmol) with 1M DIBAH in hexane (9.9 ml, 9.9 mmol) is performed as described in example 7. Chromatography of the crude product mixture on silica gel (hexane/Et 2 O 7:1) leads, after recrystallization from Et 2 O/hexane, to pure carbaldehyde 15b (0.45 g, 30%) and lactone 22b (0.90 g, 64%). Carbaldehyde 15b : m.p. 138.4 - 140.0°C.
- Heptalene 16a and 16b Carbaldehyde 15b (0.25 g, 0.55 mmol) and cinnamyl-triphenylphosphonium bromide (1.50 g, 3.30 mmol) are reacted in the two-phase system CH 2 Cl 2 /2N NaOH (30 ml/30 ml) as described in example 3. Chromatography on silica gel (hexane/Et 2 O 9:1) leads to a 1:0.37:0.07:0.07 mixture of cis- 16b : 16b : 16a :cis- 16a (0.14 g, 50%).
- the four isomers are characterized by the 1 H-NMR signals (CDCl 3 ) of their MeOCO group: 3.71 (s, 16b ), 3.64 (s, 16a ), 3.61 (s, cis- 16a ), 3.56 (s, cis- 16b ).
- Example 10 Preparation of methyl 6-methyl-9-iso-propyl-[1-(E)-(2-(p-methoxy)phenylethenyl)-4-(E)-4-(p-nitro)-phenyl-butandienyl]heptalene-5-carboxylate (21a/21b) and its DBS-isomer
- Phosphonate 17 b is dissolved in THF (20 ml) and cooled to -78°C. To this solution sodium bis(trimethylsilyl) amide (0.60 g, 3.3 mmol) in THF (10 ml) is added. After 1 h stirring at -78°C, 4-methoxybenzaldehyde (2.3 ml, 16.8 mmol) is added and the temperature raised to -18°C. At this temperature stirring is continued for 20 h. The reaction mixture is neutralized with 2N HCl and extracted with Et 2 O. The Et 2 O extracts are washed with water and dried (Na 2 SO 3 ).
- Pseudo-ester 19b Diester 18b (0.95 g, 2.07 mmol) is saponified with LiOH ⁇ H 2 O (1.90 g, 45 mmol) in MeOH (76 ml) and H 2 O (10 ml) as described in example 9. The 4-carboxylic acid of 18b is obtained in 72% yield.
- Carbaldehyde 20b Pseudo-ester 19b (2.00 g, 4.40 mmol) is dissolved in toluene (150 ml) and cooled to -78°C. At this temperature, a 2M DIBAH solution in hexane (2.2 ml, 4.40 mmol) is added dropwise under stirring. After additional stirring for 15 min, the reaction mixture is added to pre-cooled MeOH (50 ml) and then warmed up to room temperature. A small amount of H 2 O (13.2 mmol) is added and the precipitated Al salts are filtered off and washed with Et 2 O. The filtrate is dried (Na 2 SO 4 ) and evaporated.
- Heptalene 21a and 21b Carbaldehyde 20b (0.150 g, 0.35 mmol) and p-Nitrobenzyl-triphenylphosphonium bromide (1.6 g, 3.5 mmol) are reacted in the two-phase system CH 2 Cl 2 /2N NaOH (15 ml/15 ml) as described in example 3. Chromatography on silica gel (hexene/Et 2 O 4:1) gives in a first fraction the thermal equilibrium mixture of 14% of 21a and of 86% of 21b (5 mg, 2.6%).
- the UV/VIS spectra of 21a and 21b are shown in figures 2A and 2B.
- the habitus of the spectrum of 21a resembles very much that of 16a.
- the main absorption band of 21a at 340 nm is appreciably broader than that of 16a at 345 nm. This is chiefly due to the fact that the heptalene band II of 21a is much more intense than in 16a.
- the heptalene band I of 21a at ca. 440 nm seems to be more intense than in 16a.
- an additional absorption band is recognizable in 21a sitting as a shoulder on the low-wavelength flank of the heptalene band III.
- a comparable band in 16a at 280 nm is much less intense.
- the switch of the p-bonds in 21a induces again a tremendous change in the UV/VIS spectrum of the new heptalene 21b.
- the most intense band appears now at 445 nm. It must have its origin in the heptalene band I and, possibly, II (vide supra).
- the strong absorption at 375 nm can be assigned to the heptalene band III, followed by a shoulder at the low-wavelength flank at ca. 330 nm which may correlate with the shoulder at ca. 300 nm of 21a.
- Example 11 Method to prepare a rewritable compact disk comprising compounds 16a/16b as material for data storing
- a polycarbonate disk having a diameter of 5.25 inch and a thickness of 2 mm is coated with a 0.25 ⁇ m solid layer of 16a/16b by evaporating a mixture of 16a/16b in a high vacuum chamber onto its surface, thus affording an absorbence A at approximately 1 at 440 nm, as referred to 100% conjugative on-state.
- a second disk is coated by standard procedures with an Al 2 O 3 protected reflective aluminum layer. The two disks are bonded together with the heptalene and aluminum layers at the inside of the sandwich structure. Writing (bleaching) of the disk is performed by focusing a modulated IR-laser onto the heptalene layer while simultaneously irradiating the heated spot by light in the 430 to 550 nm range.
- the intensity of the IR-laser is adjusted so as to impart sufficient conformational mobility to the heptalene system 16a/16b for the photochemically induced DBS process to occur.
- Erasing coloring is achieved by irradiating a spot, which is heated as described above for increasing the mobility of the heptalene molecules being at the conjugation off-state by light having a wavelength of 350 nm or by simply recreating the 16a/16b by spotwise heating with a modulated IR-laser.
- the process is perfectly analogous for writing/erasing procedures of the traditional and well-known magneto-optical disks and similar considerations for spot size, spinning speed, guiding the write/read head, and data transfer rates apply.
- Reading of the data is achieved by focusing the light of a read laser with light in the 430 to 550 nm range of the spinning disk and registering the intensity modulation of the light reflected from the aluminum layer.
- a doubling of the data density on the disk can be achieved by using two orthogonal directions of linear polarized writing light and separately detecting the reflected intensity of two orthogonal polarizations of the reading light.
- Example 12 Method to prepare a rewritable compact disk comprising compounds 21a/21b as material for data storing
- a glass disk having a diameter of 5.25 inch and a thickness of 2 mm is coated with a 0.5 mm solid layer of a 10 -3 molar solution of 21a/21b in methylene chloride, thus affording a solid layer of heptalene molecules with an absorbence A of approximately 1 at 440 nm, as referred to 100% conjugative on-state.
- a second disk is coated by standard procedures with an Al 2 O 3 protected reflective aluminum layer. The two disks are bonded together with the heptalene and aluminum layers at the inside of the sandwich structure. Writing, erasing and reading is accomplished as in example 11.
- Example 13 Method to prepare a rewritable compact disk comprising compounds 21a/21b, embedded in a methylacrylate matrix, as material for data storage
- a 10 -3 molar solution of 21a/21b in methylene chloride is prepared in a degassed two-component or light curable methylmethacrylate embedding mass.
- the mass is sandwiched as a 2 ⁇ m thick layer between two 5.25 inch, 2 mm thick glass disk, with one of the disks coated with an Al 2 O 3 protected reflective aluminum layer turned to the inside of the sandwich structure. After the curing, writing, erasing and reading are performed as described in example 11.
- Example 14 Method to prepare a holographic rewritable memory comprising compounds 21a/21b , as material for data storage
- a 5 x 10 -3 molar concentration of 21a/21b is prepared in a degassed two-component or light-curable methylmethacryalate embedding mass.
- a volume holographic disk is prepared by coating a 3.5 inch glass disk with a 100 ⁇ m thick layer of the embedding mass containing the heptalene molecules.
- a spatially modulated object beam with a wavelength being at 450 nm is created in the usual manner by passing it through a liquid crystal spatial light modulator of 640 x 480 pixels, thus carrying about 307'200 bits of information. Said object beam is brought to interference with a reference beam of identical wavelength of approximately 1.5 mm 2 on the 10 ⁇ m layer containing the heptalene molecules.
- the spot is temporarily heated by an IR-laser to a temperature where photochemical interconversion of the conjugation on-state and off-state actually occurs, but not sizable thermal equilibration of the photochemically created conjugation on-state/off-state distribution.
- the hologram can be read out in the usual manner, by generating an object beam through irradiation of the hologram with a reference beam and recording the object beam pattern with a 640 x 480 pixel containing charge coupled device.
- Example 15 Method to prepare a spatial light modulator modulated by light and comprising compounds 16a/16b , as light modulating material
- a second signal light beam of the same or similar wave-length, linearly polarized perpendicularly to the probe beam, is combined with the latter by standard polarizing beam combining optics, so that it falls jointly with it on the entrance window of the sample cell. If the cell is made transparent - vide infra - the two superimposed beams pass jointly through the cell and are separated after the cell by standard polarizing beam splitting optics. The probe beam can thus be detected separately. Its spatial intensity distribution is analyzed by recording it with a standard light-sensitive charge-coupled (CCD) device having 640 x 480 pixels.
- CCD charge-coupled
- the signal beam before being combined with the probe beam, passes through a liquid crystal spatial light modulator having 640 x 480 pixels. If all pixels are shut-off the CCD device will record essentially zero intensity in the probe beam. If individual pixels, or contiguous clusters of pixels are turned on, the light intensity of the signal beam combines with the light intensity of the probe beam at the corresponding areas of the heptalene containing sample cell, a higher proportion of the heptalene molecules is present in the off-state at these locations, more light of the probe beam passes through the cell and is detected by the CCD device.
- the signal beam imprints its spatial intensity distribution on the probe beam. If the probe and the signal have their own spatial intensity distribution, the function performed by the cell corresponds to a logical "AND".
- a self-switching of the probe beam is achieved, i.e. an optical flip-flop.
- the polarizing beam and splitting optics are replaced by non-polar optics and the signal beam at the entrance of the sample cell is generated by the portion split of the probe after it has left the sample cell.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
- Optical Record Carriers And Manufacture Thereof (AREA)
Description
whereby said [4n]-heptalenes can comprise at least one further substituent R being selected from the above indicated groups with n being 0-8,
provided that if one of the at least one fur-ther substituents R is an isopropyl group at the position 9 of the heptalene ring, the substituent at the position 6 must not be a methyl group, and
with the proviso that heptalenes having the following formulae including their valence isomers are excluded: wherein Ar1 is phenyl, 4-chloro phenyl or 4-methoxy phenyl, wherein Ar2 is phenyl or 4-methoxy phenyl and
wherein R1' and R2' are alkyl, aralkyl or aryl, which may be substituted, but the case wherein R1' and R2' are both alkyl is excluded and R3' and R4' are hydrogen, halogen, alkyl or alkoxy and a method for the preparation of substituted heptalenes of the formula (I) or (II), whereby C1, C2, R and n are as above defined,
comprising the steps of
Claims (26)
- Method for information storage and data processing comprising the step of thermo-inducing or photo-inducing double-bond shifts (DBS) in substituted [4n]-annulenes which are substituted by at least one group comprising an extended conjugated π-electron system which is in conjugation with the π-electron system of the [4n]-annulene core, thus generating transitions between two different conjugation states with at least one substituent.
- Method according to claim 1, whereby the two different conjugation states are the conjugation on-state and conjugation off-state of the annulene core π-electrons relative to the substituent π-electrons.
- Method according to claim 1 or 2, whereby said [4n]-annulenes are bicyclic [4n]-annulenes.
- Method according to claim 3, whereby said bicyclic [4n]-annulenes are heptalenes.
- Method according to claim 4, whereby the [4n]-annulenes are substituted in 1,2- or 1,4-position relative to each other by two groups having an extended and conjugated π-electron system.
- Method according to any of the preceeding claims, whereby a multitude of [4n]-annulene molecules are arranged in a 1-dimensional or in a 2-dimensional or in a 3-dimensional way and wherein said conjugation states are spacially non-uniformly modulated.
- Method according to claim 6, whereby a conformationally restricted matrix system is generated by modulating said conjugation states.
- Method according to any of the preceeding claims, whereby the [4n]-annulene molecules are embedded in a matrix.
- Method according to claim 8, wherein the matrix comprises a low-melting glass or polycarbonates, polyacetates, methacrylates, styrenes and copolymers thereof, as well as copolymers with polymerisable [4n]-annulenes.
- Method according to any of the claims 6 - 9, whereby a holographic grating is generated by modulating said conjugation states.
- Method according to any of the claims 6 - 10, wherein the spacially non-uniformly modulated conjugation states are generated by a low-energy laser that provides for a local heating so bring the [4n]-annulenes into switching condition and whereby the laser light causes locally, if required, the switch from the conjugative on-state to the conjugative off-state.
- Method according to any of the claims 5-11, comprising further to said step of modulating a multitude of [4n]-annulene molecules in a 1-dimensional or 2-dimensional or 3-dimensional way and wherein said conjugation states are spacially non-uniformly modulated, a further step wherein at least one of the optical, electrical or magnetic properties being attributable to said switchable conjugation states is determined and processed.
- Method according to any of the preceeding claims, wherein said conjugation states are determined by an optical read-out step.
- Method according to any of the preceeding claims, wherein the determination of the spacially non-uniformly modulated conjugation states is used for the optical reading of information.
- Method according to any of the preceeding claims, wherein the determination of the spacially non-uniformly modulated conjugation states is used for optical switching and computing.
- Substituted [4n]-heptalenes of the general formula (I) or (II) being optically and/or thermally switchable, based on thermal or photochemical double-bond shifts (DBS), whereby C1 and C2 represent independently from each other a hydrogen atom, a substituted or unsubstituted C1-C12-alkyl group, a substituted or unsubstituted C1-C12-alkoxy group, a substituted or unsubstituted aryl-C1-C12-alkyl group, a substituted or unsubstituted C1-C12-alkenyl group, a substituted or unsubstituted C1-C12-conjugated alkenyl group, a substituted or unsubstituted C1-C12-alkinyl group, a substituted or an unsubstituted phenyl group, a substituted or an unsubstituted heterocyclic group, a cyano group, a nitro group, a thiocyanate group, a C1-C12-ester group being optionally polymerisable with copolymers, with the proviso that at least one of said substituents C1 and C2 contains an extended conjugated π-electron system which is in conjugation with the π-electron system of the heptalene core, and whereby said [4n]-heptalenes can comprise at least one further substituent R being selected from the above indicated groups with n being 0-8,
provided that if one of the at least one further substituents R is an isopropyl group at the position 9 of the heptalene ring, the substituent at the position 6 must not be a methyl group, and
with the proviso that heptalenes having the following substituents including their valence isomers are excluded: wherein Ar1 is phenyl, 4-chloro phenyl or 4-methoxy phenyl, wherein Ar2 is phenyl or 4-methoxy phenyl and and
wherein R1' and R2' are alkyl, aralkyl or aryl, which may be substituted, but the case wherein R1' and R2' are both alkyl is excluded and R3' and R4' are hydrogen, halogen, alkyl or alkoxy. - [4n]-heptalenes according to claim 16, whereby, C1 and C2 represent independently from each other a hydrogen atom, a methyl group, a phenyl group, an ethyl ester group, a methyl ester group, a (E)-PhCH=CH-group, a (E)-4-MeOC6H4CH=CH-group, a (E)-4-ClC6H4CH=CH-group, a 4-MeOC6H4-group, a -CH=CH-CH=CH-C6H5 group, a -CH=CH-C6H4NO2-4 group, a -CH=CH-C6H4OMe-4 group, with the proviso that a heptalene being substituted by a methyl ester group at the position 1, a -CH=CH-CH=CH-C6H5 group at the positions 2 and 5, an isopropyl group at the position 7 and a methyl group at the position 10 is excluded.
- [4n]-heptalenes according to claim 16 or 17, whereby said further substituents R are selected from the group comprising substituted or unsubstituted C1-C12-alkyl groups or photoactive diazo-containing groups, like azobenzene.
- Method for the preparation of substituted heptalenes of the formula (I) or (II), according to anyone of claims 16 - 18 whereby C1, C2, R and n are as above defined, comprising the steps of(a) obtaining a heptalene-dicarboxylate by a reaction of a correspondingly substituted azulene with acetylenedicarboxylate, and optionally(b) transforming at least one carboxylic group or another substituent that was entered by the preliminary Diels-Alder reaction, into the desired conjugated substituent having an extended π-electron system.
- Method according to claim 19, whereby a heptalene-4,5-dicarboxylate carrying a methyl substituent at the position 1 of the heptalene ring is obtained.
- Method according to claim 19 or 20, further comprising a step (c) wherein at least one of the carboxylate groups within the heptalene ring is replaced by a conjugated substituent containing an extended π-electron system.
- Method according to claim 21, wherein the carboxylate group at the position 4 of the heptalene ring is replaced by a conjugated substituent containing an extended π-electron system.
- An optical storage device comprising at least one substituted [4n]-annulene according to anyone of claims 16 - 18.
- A non-linear optical device comprising at least one substituted [4n]-annulene according to anyone of claims 16 - 18.
- Use of the substituted [4n]-annulenes which are substituted by at least one group comprising an extended conjugated π-electron system which is in conjugation with the π-electron system of the [4n]-annulene core undergoing thermally induced or photo-induced double-bond shifts (DBS) thus generating two different conjugation states with at least one substituent.
- Substituted [4n]-annulenes according to claim 16, wherein at least one of the groups C1, C2 or R is a group -COO-(CH2)nOH, a group -COO-(CH2)nOOC-C(CH3)=CH2 or a group -COO-(CH2)nC6H4-4-CH=CH2 wherein n ≥ 2.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/IB1996/001410 WO1998026412A1 (en) | 1996-12-10 | 1996-12-10 | Double-bond shifts of substituted (4n)-annulenes for information storage and data processing |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0944899A1 EP0944899A1 (en) | 1999-09-29 |
EP0944899B1 true EP0944899B1 (en) | 2002-08-07 |
Family
ID=11004504
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP96940064A Expired - Lifetime EP0944899B1 (en) | 1996-12-10 | 1996-12-10 | Double-bond shifts of substituted (4n)-annulenes for information storage and data processing |
Country Status (5)
Country | Link |
---|---|
US (1) | US6924082B1 (en) |
EP (1) | EP0944899B1 (en) |
AU (1) | AU7705996A (en) |
DE (1) | DE69622891T2 (en) |
WO (1) | WO1998026412A1 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8577772B2 (en) * | 2004-10-27 | 2013-11-05 | Itg Software Solutions, Inc. | System and method for generating liquidity |
US8450028B2 (en) * | 2011-03-29 | 2013-05-28 | Sabic Innovative Plastics Ip B.V. | Holographic storage method |
US9993172B2 (en) | 2013-12-09 | 2018-06-12 | Medtronic, Inc. | Noninvasive cardiac therapy evaluation |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59182460A (en) * | 1983-04-01 | 1984-10-17 | Canon Inc | Electrophotographic sensitive body |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0497242A (en) * | 1990-08-10 | 1992-03-30 | Sharp Corp | Information recording and reproducing method |
JPH05196973A (en) * | 1991-09-12 | 1993-08-06 | Sumitomo Electric Ind Ltd | Optical switch |
-
1996
- 1996-12-10 WO PCT/IB1996/001410 patent/WO1998026412A1/en active IP Right Grant
- 1996-12-10 DE DE69622891T patent/DE69622891T2/en not_active Expired - Fee Related
- 1996-12-10 EP EP96940064A patent/EP0944899B1/en not_active Expired - Lifetime
- 1996-12-10 AU AU77059/96A patent/AU7705996A/en not_active Abandoned
- 1996-12-10 US US09/319,566 patent/US6924082B1/en not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59182460A (en) * | 1983-04-01 | 1984-10-17 | Canon Inc | Electrophotographic sensitive body |
Non-Patent Citations (4)
Title |
---|
BULL. CHEM. SOC.JPN., vol. 61, pp.155-163 (1988) HAFNER et al. * |
CHIMIA, vol. 50 (1996) no. 7/8, page 341, abstract 151, HANSEN et al., Synthesis of New Photo- and Thermochromic Systems Based on Cyclic Double Bond Shifts in Heptalenes * |
HELVETICA CHIMICA ACTA, vol.70, pp.1439-1460 (1987) HANSEN et al. * |
PATENT ABSTRACTS OF JAPAN vol. 009, no. 044 (P - 337) 23 February 1985 (1985-02-23) * |
Also Published As
Publication number | Publication date |
---|---|
EP0944899A1 (en) | 1999-09-29 |
AU7705996A (en) | 1998-07-03 |
WO1998026412A1 (en) | 1998-06-18 |
DE69622891T2 (en) | 2003-04-30 |
DE69622891D1 (en) | 2002-09-12 |
US6924082B1 (en) | 2005-08-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6267913B1 (en) | Two-photon or higher-order absorbing optical materials and methods of use | |
Irie | Photochromic diarylethenes for photonic devices | |
US8124299B2 (en) | Methods for using optical data storage media | |
WO1998021521A9 (en) | Two-photon or higher-order absorbing optical materials and methods of use | |
Fukaminato et al. | Three-dimensional erasable optical memory using a photochromic diarylethene single crystal as the recording medium | |
Morimoto et al. | Polymorphism of 1, 2‐Bis (2‐methyl‐5‐p‐methoxyphenyl‐3‐thienyl) perfluorocyclopentene and Photochromic Reactivity of the Single Crystals | |
JP5705480B2 (en) | Composition, optical data storage medium and method of using optical data storage medium | |
US20030174560A1 (en) | Photochromic compounds for molecular switches and optical memory | |
US6737143B2 (en) | Optical recording medium, optical recording method and optical recording device | |
EP0944899B1 (en) | Double-bond shifts of substituted (4n)-annulenes for information storage and data processing | |
TW201221566A (en) | Use of appended dyes in optical data storage media | |
Wortmann et al. | A novel sensitized photochromic organic glass for holographic optical storage | |
US20110137064A1 (en) | Methacrylate-bound photoisomerizable chromophore, methods for its synthesis | |
JP2005325087A (en) | Diarylethene-based compound, photochromic material and optical function element | |
JP2001048875A (en) | Photochromic compound and optical function element using the same | |
Żmija et al. | New organic photochromic materials and selected applications | |
Towns | Fulgide dyes | |
JP2007039588A (en) | Subporphyrin compound, process for its production and its application | |
JP4132930B2 (en) | Optical recording medium and optical recording / reproducing method | |
JP2006142666A (en) | Coloring matter for optical recording medium | |
JP2004277416A (en) | Diarylethene-based compound, photochromic material, and optical functional element | |
CN1329391C (en) | Organic photochromic diaryl ethylene compound and its preparation process and application | |
JP2001151769A (en) | Photochromic compound and optical functional element using the same | |
JP3169845B2 (en) | Optical recording medium and optical head | |
Tomasulo | Photochromic materials for digital processing and sensing |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19990705 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): CH DE FR GB IT LI NL |
|
17Q | First examination report despatched |
Effective date: 20010612 |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): CH DE FR GB IT LI NL |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REF | Corresponds to: |
Ref document number: 69622891 Country of ref document: DE Date of ref document: 20020912 |
|
ET | Fr: translation filed | ||
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20030508 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20051116 Year of fee payment: 10 Ref country code: CH Payment date: 20051116 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20051118 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20051123 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20061123 Year of fee payment: 11 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20061231 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20061231 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20061231 Year of fee payment: 11 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070701 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20061210 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 20070701 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20070831 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20061210 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070102 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20080701 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20071210 |